Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104000241/ty1002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104000241/ty1002Isup2.hkl |
CCDC reference: 235335
Diethyl (Z,Z)-3,3'-(1,2-ethanediyldinitrilo)dibut-2-enoate was prepared by the condensation of 1,2-diaminoethane and ethyl acetoacetate (molar ratio 1:2) in alcohol at room temperature. The product was recrystallized from dichloromethane (yield 92%, m.p. 399–401 K). Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 8.59 (s, 2H, NH), 4.43 (s, 2H, ═CH), 4.02 (q, J = 15 Hz, 4H, ethyl CH2), 3.31 (d, J = 6 Hz, 4H, ethylene CH2), 1.86 (s, 6H, CH3), 1.19 (t, J = 15, 6H, ethyl CH3).
H atoms were constrained to their parent atoms using a riding model, with C—H distances in the range 0.93–0.96 Å and N—H distances of 0.86 Å, and with Uiso(H) = 1.2 or 1.5 times Ueq of the parent atom. Please check added text.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
C14H24N2O4 | Dx = 1.253 Mg m−3 |
Mr = 284.35 | Melting point = 399–401 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.505 (2) Å | Cell parameters from 1735 reflections |
b = 10.540 (2) Å | θ = 2.7–25.8° |
c = 13.471 (3) Å | µ = 0.09 mm−1 |
β = 112.66 (3)° | T = 293 K |
V = 1507.4 (6) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
F(000) = 616 |
Bruker SMART CCD area-detector diffractometer | 1325 independent reflections |
Radiation source: fine-focus sealed tube | 1147 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→13 |
Tmin = 0.973, Tmax = 0.982 | k = −12→11 |
3026 measured reflections | l = −15→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0925P)2 + 4.2899P] where P = (Fo2 + 2Fc2)/3 |
1325 reflections | (Δ/σ)max < 0.001 |
91 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
C14H24N2O4 | V = 1507.4 (6) Å3 |
Mr = 284.35 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.505 (2) Å | µ = 0.09 mm−1 |
b = 10.540 (2) Å | T = 293 K |
c = 13.471 (3) Å | 0.30 × 0.20 × 0.20 mm |
β = 112.66 (3)° |
Bruker SMART CCD area-detector diffractometer | 1325 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1147 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.982 | Rint = 0.032 |
3026 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.50 e Å−3 |
1325 reflections | Δρmin = −0.49 e Å−3 |
91 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1214 (2) | 0.1390 (2) | 0.02196 (17) | 0.0414 (6) | |
O2 | 0.0420 (2) | 0.3379 (2) | 0.00038 (17) | 0.0434 (7) | |
N1 | 0.0909 (2) | 0.4645 (2) | 0.1940 (2) | 0.0356 (7) | |
H1A | 0.0699 | 0.4735 | 0.1258 | 0.043* | |
C1 | 0.1345 (3) | 0.0067 (3) | −0.1154 (3) | 0.0476 (9) | |
H1B | 0.1117 | −0.0025 | −0.1915 | 0.071* | |
H1C | 0.0995 | −0.0622 | −0.0893 | 0.071* | |
H1D | 0.2246 | 0.0058 | −0.0796 | 0.071* | |
C2 | 0.0842 (3) | 0.1302 (3) | −0.0931 (3) | 0.0431 (8) | |
H2A | 0.1187 | 0.2006 | −0.1192 | 0.052* | |
H2B | −0.0069 | 0.1322 | −0.1287 | 0.052* | |
C3 | 0.0976 (3) | 0.2514 (3) | 0.0603 (2) | 0.0358 (7) | |
C4 | 0.1481 (3) | 0.2512 (3) | 0.1761 (2) | 0.0357 (7) | |
H4A | 0.1864 | 0.1774 | 0.2115 | 0.043* | |
C5 | 0.1429 (3) | 0.3534 (3) | 0.2370 (2) | 0.0338 (7) | |
C6 | 0.2051 (3) | 0.3430 (3) | 0.3576 (2) | 0.0422 (8) | |
H6A | 0.1937 | 0.4209 | 0.3897 | 0.063* | |
H6B | 0.2934 | 0.3270 | 0.3781 | 0.063* | |
H6C | 0.1676 | 0.2745 | 0.3819 | 0.063* | |
C7 | 0.0665 (3) | 0.5711 (3) | 0.2515 (2) | 0.0349 (7) | |
H7A | 0.0807 | 0.6495 | 0.2201 | 0.042* | |
H7B | 0.1256 | 0.5685 | 0.3258 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0543 (14) | 0.0363 (12) | 0.0343 (12) | 0.0070 (10) | 0.0179 (10) | −0.0005 (9) |
O2 | 0.0535 (14) | 0.0387 (13) | 0.0376 (12) | 0.0104 (10) | 0.0170 (11) | 0.0035 (10) |
N1 | 0.0400 (14) | 0.0383 (14) | 0.0309 (13) | 0.0051 (11) | 0.0162 (11) | 0.0027 (10) |
C1 | 0.057 (2) | 0.045 (2) | 0.0422 (19) | 0.0065 (16) | 0.0207 (15) | −0.0047 (15) |
C2 | 0.0520 (19) | 0.0411 (18) | 0.0362 (17) | 0.0052 (15) | 0.0171 (14) | −0.0012 (14) |
C3 | 0.0388 (16) | 0.0328 (16) | 0.0392 (17) | 0.0009 (13) | 0.0188 (13) | −0.0005 (13) |
C4 | 0.0377 (15) | 0.0356 (16) | 0.0344 (16) | 0.0051 (13) | 0.0145 (12) | 0.0033 (12) |
C5 | 0.0316 (14) | 0.0369 (17) | 0.0342 (16) | 0.0020 (12) | 0.0141 (12) | 0.0038 (12) |
C6 | 0.0506 (18) | 0.0424 (18) | 0.0326 (17) | 0.0048 (15) | 0.0151 (14) | 0.0024 (13) |
C7 | 0.0399 (16) | 0.0301 (15) | 0.0367 (16) | 0.0006 (12) | 0.0169 (13) | −0.0002 (12) |
O1—C3 | 1.362 (4) | C2—H2B | 0.9700 |
O1—C2 | 1.443 (4) | C3—C4 | 1.439 (4) |
O2—C3 | 1.222 (4) | C4—C5 | 1.370 (4) |
N1—C5 | 1.342 (4) | C4—H4A | 0.9300 |
N1—C7 | 1.452 (4) | C5—C6 | 1.505 (4) |
N1—H1A | 0.8600 | C6—H6A | 0.9600 |
C1—C2 | 1.501 (4) | C6—H6B | 0.9600 |
C1—H1B | 0.9600 | C6—H6C | 0.9600 |
C1—H1C | 0.9600 | C7—C7i | 1.515 (6) |
C1—H1D | 0.9600 | C7—H7A | 0.9700 |
C2—H2A | 0.9700 | C7—H7B | 0.9700 |
C3—O1—C2 | 116.3 (2) | C5—C4—C3 | 123.7 (3) |
C5—N1—C7 | 126.2 (3) | C5—C4—H4A | 118.1 |
C5—N1—H1A | 116.9 | C3—C4—H4A | 118.1 |
C7—N1—H1A | 116.9 | N1—C5—C4 | 122.9 (3) |
C2—C1—H1B | 109.5 | N1—C5—C6 | 118.5 (3) |
C2—C1—H1C | 109.5 | C4—C5—C6 | 118.5 (3) |
H1B—C1—H1C | 109.5 | C5—C6—H6A | 109.5 |
C2—C1—H1D | 109.5 | C5—C6—H6B | 109.5 |
H1B—C1—H1D | 109.5 | H6A—C6—H6B | 109.5 |
H1C—C1—H1D | 109.5 | C5—C6—H6C | 109.5 |
O1—C2—C1 | 107.1 (3) | H6A—C6—H6C | 109.5 |
O1—C2—H2A | 110.3 | H6B—C6—H6C | 109.5 |
C1—C2—H2A | 110.3 | N1—C7—C7i | 112.7 (2) |
O1—C2—H2B | 110.3 | N1—C7—H7A | 109.0 |
C1—C2—H2B | 110.3 | C7i—C7—H7A | 109.0 |
H2A—C2—H2B | 108.6 | N1—C7—H7B | 109.0 |
O2—C3—O1 | 121.9 (3) | C7i—C7—H7B | 109.0 |
O2—C3—C4 | 127.4 (3) | H7A—C7—H7B | 107.8 |
O1—C3—C4 | 110.7 (3) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H24N2O4 |
Mr | 284.35 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.505 (2), 10.540 (2), 13.471 (3) |
β (°) | 112.66 (3) |
V (Å3) | 1507.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.973, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3026, 1325, 1147 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.206, 1.07 |
No. of reflections | 1325 |
No. of parameters | 91 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.49 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
O1—C3 | 1.362 (4) | C3—C4 | 1.439 (4) |
O2—C3 | 1.222 (4) | C4—C5 | 1.370 (4) |
N1—C5 | 1.342 (4) | ||
C5—N1—C7 | 126.2 (3) | N1—C5—C4 | 122.9 (3) |
O2—C3—C4 | 127.4 (3) | N1—C5—C6 | 118.5 (3) |
O1—C3—C4 | 110.7 (3) | C4—C5—C6 | 118.5 (3) |
C5—C4—C3 | 123.7 (3) |
The condensation reaction of ethylenediamine with ethyl acetoacetate, catalyzed by various Friedel-Crafts-type catalysts, gives the open chain compound (I) (Moazzam et al., 1988). However, we found that the reaction occurs easily without any catalyst and yields a crystalline product that was originally thought to have the structure of (I). However, 1H NMR suggested that there are two vinyl H atoms (δ 4.43, s) and two H atoms on the N (δ 8.59, s), and that the structure is thus in fact (II) (Costes & Laurent, 1988). \sch
Although structure (II) is strongly supported by 1H NMR spectroscopy, there are still some questions regarding its conformation and configuration. In addition to verifying structure (II), X-ray analysis of the compound has now been undertaken and the results are presented here (Fig. 1).
The ethylenediamine structural unit in this molecule adopts a low-energy gauche conformation with respect to the central C7—C7A bond, which is very similar to 1,2-ethanediamine (Burgess et al., 1976; Marstokk & Mοllendal, 1978). The molecule adopts a `twist' conformation, with an N1—C7—C7A—N1A torsion angle of 66°, and the C4═C5 bond is in the (Z,Z) configuration.
The N1—C5 bond length of 1.342 (4) Å is shorter than the standard N—C experimental bond length of 1.469 Å (Lice, 1957). This large difference is considered to be the result of π–π conjugation between the N atom and the C═C bond. Conversely, the C3═O2 bond [1.222 (4) Å] is longer than that in other derivative compounds [e.g. 1.199 (3) Å; Balsamini et al., 1992]. The O2—C3—C4—C5 torsion angle is −1.7°, indicating that the π–π conjugation is spread between the C═C bond and the C═O (ester) bond.
Another interesting characteristic of (II) is its (Z,Z) configuration, which is probably caused and stabilized by intramolecular N—H···O═C hydrogen bonds (Fig.2 and Table 2) (Jeffrey, 1997).